CN105008424A - Two-component coating composition - Google Patents
Two-component coating composition Download PDFInfo
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- CN105008424A CN105008424A CN201480012501.XA CN201480012501A CN105008424A CN 105008424 A CN105008424 A CN 105008424A CN 201480012501 A CN201480012501 A CN 201480012501A CN 105008424 A CN105008424 A CN 105008424A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/588—Epoxy resins having silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/542—No clear coat specified the two layers being cured or baked together
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to a coating composition comprising (A) at least one polyaspartic acid ester, (B) at least one polyisocyanate cross-linking agent with free isocyanate groups and (C) at least one compound with at least one epoxy group and at least one alkoxy silane group and to the use of the coating composition as primer, primer surfacer, pigmented single stage top coat or clear coat coating composition, particularly in vehicle repair coating.
Description
The cross reference of related application
This application claims the right of priority of No. 61/773,373, the U.S. Provisional Application submitted on March 6th, 2013.
Technical field
The disclosure relates to double-component paint composition, and this double-component paint composition comprises isocyanate-reactive component and polyisocyanate curing agent.Coating composition of the present invention especially can be used as Clearcoat coating composition in the method producing laminated coating, and the method can be particularly useful for coating vehicles body and vehicles body part.
Background technology
Coating composition based on aspartate (aspartate) is known in the field.Such as, EP 0403921 describes the coating composition containing tackiness agent, and it is based on polyisocyanate component and the isocyanate-reactive component containing specific secondary polyamine.These secondary polyamines are also referred to as polyaspartate (polyaspartic acid ester), and are the reaction product of diester based on uncle's polyamines and toxilic acid and/or fumaric acid.
EP 0470461 also illustrates the coating composition for vehicle repairing application, this coating composition contains polyisocyanate component and isocyanate-reactive secondary diamine, this isocyanate-reactive secondary diamine is by 3,3 '-dimethyl 4, prepared by 4 '-diamino-dicyclohexyl methane and ethyl maleate.This isocyanate-reactive component contains hydroxyl functional binder that is that be made up of poly-(methyl) acrylate or that be made up of the mixture gathering (methyl) acrylate and polyester polyol further.
The shortcoming of the above-mentioned coating composition based on aspartate is: although these coating compositions have fast curing times, but the shelf life (pot life) that these coating compositions still can not provide suitable is applied for some, namely, before being applied to base material after the components are mixed and by this coating composition, the viscosity of these compositions increases too fast.In addition, these coating compositions based on the mixture of aspartate and polyvalent alcohol and aspartate cause yellow in tank (pot), and due to the mixing of polyisocyanates, and acceptable interlaminar adhesion can not be provided in multilayered structure.The coating of Clearcoat coating composition on photo tint base coating coating composition containing aspartate especially lacks adhesivity.The alcohol resistance that aforementioned coating composition with the further shortcoming of the coating obtained is is very poor.
In addition, WO 2010/112157 discloses a kind of protection against corrosion priming paint, and this protection against corrosion priming paint contains polyaspartate and silane-functional polyisocyanates.
WO 2009/086026 discloses a kind of Clearcoat coating composition based on transparent organic solvent, this Clearcoat coating composition comprises at least one tackiness agent, at least one polyisocyanate crosslinker and at least one epoxy functional silane, wherein, described tackiness agent has the functional group's (especially hydroxyl) containing active hydrogen, and polyisocyanate crosslinker has free isocyanate groups.These coating compositions demonstrate outstanding sticking property.Particularly, the multilayered structure containing described Clearcoat coating composition has enough interlayer adhesions, such as, on water base undercoat, have enough interlayer adhesions.These Clearcoat coating compositions are not containing isocyanate-reactive polyaspartate.
Up to now, gratifying scheme can't be provided significantly not damage other important coating property, while such as shelf life (pot life), VOC content (VOC=volatile organic compounds), drying property, stability and the optical property of coating that obtains, improve adhesivity on base material of two-part formulations based on aspartate and polyisocyanates or interlayer adhesion.
Therefore, need to provide a kind of coating composition, especially Clearcoat coating composition, this coating composition does not have the shortcoming of two-component coating system in prior art.Particularly, need to provide a kind of quick-setting Clearcoat coating composition with acceptable shelf life, this Clearcoat coating composition does not demonstrate yellow after blending in tank, and do not demonstrate yellow at memory period based on the component of aspartate yet, and this Clearcoat coating composition produces has very outstanding wet fastness and adhesivity (such as gratifying wet interlayer adhesion and dry interlayer adhesion, especially at first coating such as water base primary coating composition layer, there is very outstanding initial wet adhesivity and dry adhesivity) coating.In addition, this coating composition also will produce the coating with very good alcohol resistance.In addition, by reference to the accompanying drawings with this background technology, by general introduction hereafter and detailed description and claim, other object, required characteristic sum characteristic will become obvious.
Summary of the invention
According to illustrative embodiments, coating composition comprises:
(A) at least one polyaspartate;
(B) at least one has the polyisocyanate crosslinker of free isocyanate groups; And
(C) at least one has the compound of at least one alkoxysilane group and at least one epoxy group(ing).
Embodiment
Below describe in detail only for exemplary object, and be not intended to restriction the present invention or the application and purposes of the present invention.In addition, the constraint by background of invention above or any theory mentioned by detailed description is hereafter not meant to.
To know, for clarity sake, also can be provided in combination in single embodiment in some feature of the present invention independently described in embodiment context.On the contrary, for for purpose of brevity, the of the present invention multiple feature described in the context of single embodiment also can provide independently or in the mode of anyon combination.In addition, explicitly bright except having in non-content, otherwise the addressing thing and also can comprise plural number (such as, " (a) " and " a kind of (an) " can represent 1, or one or more) of singulative.
Herein and hereinafter used term " (methyl) vinylformic acid () " methacrylic acid () or vinylformic acid () should be represented.
Except as otherwise noted, all molecular weight (number-average molecular weight and weight-average molecular weight) described herein all utilize polystyrene as standard, and tetrahydrofuran (THF), as liquid phase elutriant, is measured by GPC (gel permeation chromatography).
Water base paint compositions is such coating composition, and wherein in preparation and/or when applying this coating composition, water is used as solvent or thinner.Usually, the total amount of coating based composition, water base paint compositions can containing the water of such as 30wt% to 90wt%, and based on the total amount of this coating composition, alternatively containing 30wt% at the most, preferably lower than the organic solvent of 15wt%.
Organic solvent based coating composition is such coating composition, and wherein in preparation and/or when applying this coating composition, organic solvent is used as solvent or thinner.Usually, the total amount of coating based composition, solvent-based coating composition contains the organic solvent of such as 10wt% to 90wt%.
Shelf life, (pot life) was for some time, and within this period, after the component reacted to each other of compo composition, this coating composition still can be properly handled or apply and can obtain the coating of unimpaired quality.
Described coating composition is double-component paint composition, that is, the component (i.e. polyaspartate (A) and polyisocyanate crosslinker (B)) that can react each other must be separated from each other before application and store to avoid premature reaction.Usually, component (A) and polyisocyanate component (B) only can just mix before the application soon.It is well known to a person skilled in the art that term " applied not long ago (shortly before application) ".The time period of the i.e. spendable coating composition can prepared before reality uses/applies is depended on, the shelf life of such as coating composition.
Component (A)
At least one polyaspartate is comprised according to a kind of coating composition of embodiment.
Preferably, at least one polyaspartate corresponding (I):
Wherein, X represents the n-valency organic group that the amino by removing in uncle's polyamines or polyetheramine obtains, and is preferably bivalent hydrocarbon radical; R1 and R2 is the identical or different organic group to isocyanate group inertia.R3, R4 and R5 are identical or different, and represent hydrogen or the organic group to isocyanate group inertia; And n represents that at least value is the integer of 2, be preferably the integer of 2 to 4, be more preferably 2.X preferably represents the bivalent hydrocarbon radical that the amino by removing in hereafter mentioned uncle's polyamines or polyetheramine obtains, and more preferably represents the bivalent hydrocarbon radical that the amino by removing hereafter preferred uncle's polyamines obtains.R1 and R2 is identical or different residue, and is preferably methyl, ethyl or normal-butyl; R3, R4 and R5 are preferably hydrogen.Preferably, be under 150 DEG C or lower temperature to the organic group of isocyanate group inertia, to the organic group of isocyanate group inertia.The polyaspartate of formula (I) is that the maleic acid ester of corresponding uncle's polyamines by making to meet formula X-(NH2) n or polyetheramine and the optional replacement meeting formula R1OOC-CR3=CR4-COOR2 or fumarate react and prepare in known manner.The implication that faced by X, R1, R2, R3, R4 and n have as above, formula (I) defines.
Uncle's polyamines or polyetheramine are preferred for preparing polyaspartate, and polyaspartate provides favourable solid substance/viscosity ratio, for 3.5 lbs/gal (lbs/gal) (420 grams per liter) met needed for end formulation or lower VOC.Uncle's polyamines or polyetheramine also react with the amount of mole excess and vulcabond and polyisocyanates urea or the polyethers urea of preparing amine end-blocking, or can to isocyanate-terminated polyester, polycarbonate or the polyether reactant obtained by corresponding polyester, polycarbonate or polyether Glycols or polyether glycol, and amido (terminal amine group) will be held to be converted into aspartate by reacting with maleic acid ester and/or fumarate subsequently.
Suitable uncle's polyamines comprises quadrol; 1，2-diaminopropane; 1,4-Diaminobutane; 1,3-1,5-DAP; 1，6-diaminohexane; 2,5-diamino-2,5-dimethylhexane; 2,2,4-trimethylammonium-1，6-diaminohexane and 2,4,4-trimethylammonium-1，6-diaminohexane; 1,11-diamino undecane; 1,12-diamino dodecane; 1,3-cyclohexanediamine and Isosorbide-5-Nitrae-cyclohexanediamine; Amino-3,3, the 5-trimethylammonium of 1--5-aminomethyl cyclohexane; 2,4-hexahydrotoluene diamines and 2,6-hexahydrotoluene diamines; 2,4'-diamino-dicyclohexyl methyl hydride and 4,4'-diamino-dicyclohexyl methyl hydride, and 3,3'-dialkyl group-4,4'-diamino-dicyclohexyl methane, such as 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane and 3,3'-diethyl-4,4'-diamino-dicyclohexyl methane; 2,4,4'-triamino-5-methyldicyclohexyl methane; 2-methyl isophthalic acid, 5-pentamethylene diamine; The sub-dimethylphenylene diamine (1,3-xylylenediamine) of 1,3-and Isosorbide-5-Nitrae-Ya dimethylphenylene diamine (Isosorbide-5-Nitrae-xylylenediamine).Preferred uncle's polyamines is amino-3,3,5-trimethylammonium-5-aminomethyl cyclohexane (IPDI); 2,4'-diamino-dicyclohexyl methyl hydride and 4,4'-diamino-dicyclohexyl methyl hydride; 3,3'-dialkyl group-4,4'-diamino-dicyclohexyl methane, such as 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methanes; And 2-methyl isophthalic acid, 5-pentamethylene diamine.
Suitable polyether polyamine is the polyether polyamine of the primary amino with aliphatics bonding.This polyether polyamine can have the molecular weight of 148 to 6000.The example of suitable polyether polyamine is with trade name
purchased from the product of Huntsman Corporation (Huntsman).
Be applicable to prepare the mixed ester that the maleic acid ester of optional replacement of polyaspartate or the example of fumarate comprise dimethyl esters, diethyl ester, dibutyl (such as di-n-butyl, di-sec-butyl, di-t-butyl) ester, diamyl ester, two-2-(ethyl hexyl) esters and the mixture based on above-mentioned group and/or other alkyl; And in 2-position and/or 3-position by methyl substituted corresponding maleic acid ester and fumarate.The dimethyl ester of preferred toxilic acid, diethyl ester and dibutylester, especially preferably diethyl ester.
Other diester spendable is for being derived from those diester of cycloaliphatic alcohol, dicyclo fatty alcohol and aromatic alcohols (such as hexalin, phenylcarbinol and iso-borneol alcohol).Also long chain monohydric alcohols can be used, such as ether alcohol, the reaction product of such as monoalkyl monohydroxy-alcohol, cycloalkyl monohydroxy-alcohol and aryl monohydroxy-alcohol and oxyethane, propylene oxide, butylene oxide ring, such as ethylene glycol monobutyl ether, ethylene glycol ether, propylene glycol monobutyl ether.
Such as at the temperature of 0 DEG C to 150 DEG C, utilization makes the starting raw material of the ratio each primary amino being existed at least one (being preferably 1) olefinic double bond, by the polyaspartate of the above-mentioned starting raw material preparation formula (I) mentioned.After reaction, remove excessive starting raw material by distillation.This reaction can be carried out in the absence of solvent or under suitable organic solvent exists, and suitable organic solvent is alcohol, ether, acetic ester and ketone (such as methyl alcohol, ethanol, propyl alcohol, n-butyl acetate, butyl glycol, methylethylketone, two such as
alkane), and the mixture of these organic solvents.Preferred solvent be not with those organic solvents of isocyanate reaction.
Component (B)
The polyisocyanate crosslinker (B component) with free isocyanate groups is comprised according to a kind of coating composition of embodiment.Polyisocyanates can for having the organic multiple isocyanate of any amount of the free isocyanate groups group of aliphatics, cyclic aliphatic, araliphatic and/or aromatic series bonding.Described polyisocyanates at room temperature becomes liquid for liquid state or by adding organic solvent.At 23 DEG C, described polyisocyanates has 1mPas to 3500mPas usually, the viscosity of preferred 5mPas to 3000mPas.
Preferred polyisocyanates for average NCO functionality be 1.5 to 6, preferably 2 to 6 the polyisocyanates only with the isocyanate groups of aliphatics and/or cyclic aliphatic bonding or polyisocyanate mixtures.
The example of specially suitable polyisocyanates is known those polyisocyanates being called " paint polyisocyanates (paintpolyisocyanates) "; it is based on hexamethylene diisocyanate (HDI), 1-isocyanato-3; 3,5-trimethylammonium-5-isocyanide acyl methyl-cyclohexyl alkane (IPDI) and/or two (isocyanatocyclohexyl)-methane and known derivative (vulcabond of biuret-containing group, allophanate groups, carbamate groups and/or isocyanurate group) itself.Typically, after the preparation, preferably by distillation, from this derivative, remove superfluous raw material vulcabond (parent diisocyanate), make residue content be less than 0.5wt%.Also triisocyanate can be used, such as three isocyanato nonanes (triisocyanatononan).
The polyisocyanates be obstructed in space is also suitable.The example of this polyisocyanates is 1,1,6,6-tetramethyl--hexamethylene diisocyanate, 1,5-dibutyl-five-methyl diisocyanate (1,5-dibutyl-penta-methyldiisocyanate), p-tetramethyl xylylen vulcabond or m-tetramethyl xylylen vulcabond and suitable hydration homologue.In principle, by ordinary method, vulcabond is converted into higher functional degree compound, such as, passes through trimerizing or react with water or polyvalent alcohol (such as TriMethylolPropane(TMP) or glycerine).This polyisocyanates also can use with the form of isocyanate-modified resin or isocyanate functional prepolymer's thing.Usually, this polyisocyanates can be isocyanuric acid ester, urea diisocyanates, the polyisocyanates (biuret group-containingpolyisocyanate) of biuret-containing base, containing the polyisocyanates (urethane group-containingpolyisocyanate) of urethane groups, the polyisocyanates (allophanate group-containingpolyisocyanate) of special allophanates containing base, containing the polyisocyanates of isocyanuric acid ester and allophanate groups, the polyisocyanates (carbodiimide group-containing polyisocyanate) of carbodiimide base and the polyisocyanates (polyisocyanates containing acylurea groups) containing uride base.
Described polyisocyanate crosslinker can be used alone or combination with one another uses.Described polyisocyanate crosslinker is those polyisocyanate crosslinkers conventional in paint industry.It is described later in detail and also commercially available acquisition in the literature.Described polyisocyanate crosslinker B) isocyanate group can be partially enclosed (blocked).Low-molecular weight compound containing the active hydrogen for closing NCO group is known.The example of these encapsulants is fatty alcohol or cycloaliphatic alcohol, dialkyl amido alcohol, oxime, lactan, imide, hydroxy alkyl ester and the ester of propanedioic acid or the ester of etheric acid.
Component (C)
The compound that at least one contains at least one alkoxysilane group and at least one epoxy group(ing) is comprised according to a kind of coating composition of embodiment.Preferably, the compound that described at least one contains at least one alkoxysilane group and at least one epoxy group(ing) is not polyaspartate, neither polyisocyanates.Compound C) can be monomeric compound, oligomeric compound or polymerizable compound.Suitable monomeric compound, oligomeric compound or polymerizable compound C) for having those compounds that at least one corresponds to the alkoxysilane group of formula (II):
Wherein, R6, R7, R8 are the organic group that identical or different per molecule has 1 to 30 carbon atom, and prerequisite is at least one in residue R6, R7 and R8 is the alkoxyl group with 1 to 4 carbon atom.
Except alkoxysilane group, monomeric compound, poly-compounds and oligomeric compound C) containing at least one epoxide group.
According to a kind of embodiment, described at least one contains the Compound C of at least one alkoxysilane group and at least one epoxy group(ing)) be monomeric compound, be preferably the compound of general formula (III):
Wherein, Z represents that m is the residue of 1 to 4
or represent 3,4-epoxycyclohexyl; R6, R7, R8 are the identical or different organic residue with 1 to 30 carbon atom, and prerequisite is at least one in residue R6, R7 and R8 is the alkoxyl group with 1 to 4 carbon atom; And n is 2,3 or 4, be preferably 2 or 3.
The preferred compound of formula (III) is that wherein Z is
those compounds of (m is 1 to 4).
In described compound, it is also preferred that, R6, R7 and R8, for having 1 to 4, preferably have the identical or different alkoxyl group of 1,2 or 3 carbon atom.Particularly preferred alkoxyl group is methoxyl group, oxyethyl group and isopropoxy.
The example of the epoxy functional silane compound of specially suitable general formula (III) is (3-epoxypropoxy) Trimethoxy silane ((3-glycidoxypropyl) trimethoxysilane), (3-epoxypropoxy) triethoxyl silane, (3-epoxypropoxy) three isopropoxy silane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane and β-(3,4-expoxycyclohexyl) ethyl triethoxysilane.
The silane with methoxyl group particularly preferably is, such as (3-epoxypropoxy) Trimethoxy silane and β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane at this.
The epoxy functional silane compound of operable formula (III) also can be used as commodity and obtains, such as, with trade name
glymo is available from Degussa company (Degussa), with trade name
a187 and
a186 is available from ACC silica gel company (ACC Silicones).
Polymeric component C) example be (methyl) acrylic copolymer ((meth) acrylic copolymer) with at least one alkoxysilane group and at least one epoxy group(ing).
Relative to component A) and B component) the summation of solid content, with solid substance weighing scale, 0.25wt% to 5.0wt% can be used, especially 0.8wt% to 3.0wt%, and the described Compound C of most preferably 2.0wt% to 3.0wt%) (particularly the preferred compound of formula (III)).If the component C used) amount with solid substance weighing scale, be greater than 5.0wt%, then can cause the poor hardness development of the poor viscosity of coating composition and colour stability and laminated coating.If the component C used) amount with solid substance weighing scale, be less than 0.25wt%, then can not realize required positively effect, especially adhesivity effect.
Except component A) except, this coating composition can comprise hydroxyl functional binder.This hydroxyl functional binder can be number-average molecular weight (Mn) and is such as 500 grams/mol to 500000 grams/mol, is preferably the compound of the oligomeric and/or polymerization of 1100 grams/mol to 100000 grams/mol.Urethane, (methyl) acrylic copolymer, polyester and polyethers in the polyurethane chemistry that the tackiness agent with hydroxyl is such as known for technician, they can be used in the formula of such as organic solvent based coating composition.They can be used alone or use in the mode of combination with one another separately.
The example of hydroxyl-functional (methyl) acrylic copolymer comprises and is applicable to organic solvent based coating composition and all (methyl) acrylic copolymers of knowing of technician.Such as, their mumber average molar mass Mn is 1000 grams/mol to 20000 grams/mol (preferably 1100 grams/mol to 15000 grams/mol), acid number is 0mg KOH/g to 100mg KOH/g, and hydroxyl value is 40mg KOH/g to 400mg KOH/g (preferred 60mg KOH/g to 200mg KOH/g).(methyl) acrylic copolymer can be prepared by Raolical polymerizable by polymerisable ethylenically unsaturated monomer, prepares alternatively under the oligomeric or polyester of polymerization and/or the existence of urethane resin.The ethylenically unsaturated monomer of spendable free redical polymerization, can be except containing except at least one olefinic double bond, can also contain the monomer of functional group further, and the monomer not containing other functional group except at least one olefinic double bond.
The example that can be used as hydroxyl-functional polyester's resin of tackiness agent comprises all vibrin being applicable to organic solvent based coating composition, such as, number-average molecular weight is 500 grams/mol to 10000 grams/mol (preferably 1100 grams/rub to 8000 grams/mol), acid number is 10mg KOH/g to 150mg KOH/g (preferred 15mg KOH/g to 50mg KOH/g), and hydroxyl value is the hydroxyl-functional polyester of 40mg KOH/g to 400mg KOH/g (preferred 50mg KOH/g to 200mg KOH/g).This polyester can be saturated or unsaturated, and they carry out modification with lipid acid alternatively.This polyester is eliminated water to prepare from polycarboxylic acid and polyvalent alcohol by currently known methods.
The example of suitable hydroxyl-functional polyurethane comprises and is applicable to coating composition and all urethane resins of knowing of technician.Example is such as number-average molecular weight is 500 grams/mol to 500000 grams/mol (preferably 1100 grams/rub to 300000 grams/mol, more preferably 5000 grams/rub to 300000 grams/mol), acid number is 0mg KOH/g to 100mg KOH/g, and hydroxyl value is the urethane of 40mg KOH/g to 400mgKOH/g (preferred 80mg KOH/g to 250mg KOH/g).Spendable suitable urethane resin is such as prepared by making to have relative to isocyanate group the polyisocyanates radical reaction that reactive compound and per molecule have at least 2 free isocyanate groups.
If except component A) except, have hydroxyl functional binder, then preferably use hydroxyl-functional (methyl) acrylic copolymer.
If except component A) except, have hydroxyl functional binder, then based on total binder solid substance (polyaspartate solid substance+hydroxyl functional binder's solid substance sum), this hydroxyl functional binder is to be less than 50wt%, and the amount of such as 5wt% to 10wt% exists.The hydroxyl value of described hydroxyl functional binder, for being less than 400mg KOH/g solid substance, is preferably 10mg KOH/g to 260mg KOH/g solid substance.
If when the amount of this hydroxyl functional binder or described hydroxyl value exceed above-mentioned value, shelf life of described coating composition to show and reduce.
Preferably, the coating composition considered herein not hydroxyl official can tackiness agent.In further embodiment, described coating composition is not containing closing amine.
Relative to the total amount (tackiness agent solid substance=aspartate solid substance+polyisocyanates solid substance) of the tackiness agent solid substance of described coating composition, with solid substance weighing scale, the coating composition considered herein preferably includes at least one polyaspartate (component A) of 20wt% to 80wt%, and at least one of 20wt% to 80wt% has the polyisocyanate crosslinker (B component) of free isocyanate groups.
Polyaspartate (A) and linking agent (B) use in the ratio of such amount: make the equivalence ratio of the isocyanate group of the secondary amine of component (A) and linking agent (B) be, such as, 5:1 to 1:5, preferred 3:1 to 1:3, particularly preferably 1.5:1 to 1:1.5.If when using hydroxyl functional binder and reactive diluent further, then need when calculating equivalents ratio the reactive functional groups considering them.
Organoalkoxysilane and epoxy functional compounds (C) can exist in one of two kinds of components in double-component paint composition or be present in two kinds of components of double-component paint composition.Most preferably, organoalkoxysilane and epoxy functional compounds (C) are present in polyisocyanate component (B).
In principle, before application, still can utilize organic solvent that this coating composition is adjusted to atomizing viscosity.In all cases, can have for generation of all further component needed for available coating composition, such as pigment, filler, organic solvent and additive in one of two kinds of components or two kinds of components of bicomponent system.
Except component (A), component (B) and component (C), the coating composition considered herein can containing the conventional constituents used in coating composition, such as pigment, filler, additive and organic solvent.Described pigment, filler, additive and organic solvent use with conventional amount used known to the skilled.
Described organic solvent can be derived from the preparation of tackiness agent or it can add separately.Described organic solvent is organic solvent that coating composition is conventional and is that technician is known.
Additive is in paint field, the particularly conventional additive used in Clear coating.The example of this additive comprises: such as based on the bright protective agent of benzotriazole and HALS compound (hindered amine as light stabilizer), based on the flow agent (leveling and flowagents) of (methyl) acrylic homopolymer or silicone oil, the such as rheology control agent (rheology-influencing agent) of fine-particle silicon dioxide or polymerization carbamide compound, defoamer, wetting agent, for curing catalysts (the such as organic metal salt of crosslinking reaction, such as dibutyl tin dilaurate, zinc naphthenate) and for hydroxyl/isocyanate reaction containing the compound (such as triethylamine) of tertiary amine groups.
The example of pigment is color-imparting pigment, such as titanium dioxide, micronized titanium dioxide, iron oxide pigment, carbon black, azo pigment, phthalocyanine pigment, quinacridone and pyrrolopyrrole pigment; And give the pigment of special efficacy, such as metallic pigment and coated interference pigment.The example of filler is silicon-dioxide, pure aluminium silicate, aluminum oxide, barium sulfate and talcum.
According to preferred implementation, described coating composition comprises:
A) at least one two aspartate (di-aspartic acid ester);
B) at least one has the polyisocyanate crosslinker of free isocyanate groups; And
C) at least one as above alkoxysilane that limits of general formula (III) and epoxy functional compounds.
Described at least one two aspartate A) be preferably the compound of the formula (I) representing 2 corresponding to n.More preferably, described at least one two aspartate A) be the compound representing the formula (I) of 2 corresponding to n, wherein X=dicyclohexyl methyl hydride (dicyclohexylmethane), R1 and R2 is identical or different residue=methyl, ethyl or normal-butyl, and R3, R4 and R5=hydrogen.
Coating composition considered herein can be used as colored coating composition, such as, as priming paint, primer surfacer, painted single-stage top coat layer (single stage top coat) or Clearcoat coating composition.According in preferred implementation, described coating composition is Clearcoat coating composition.
According to further preferred embodiment, coating composition as above is organic solvent based coating composition.
More preferably, coating composition as above is organic solvent based Clearcoat coating composition.
Preferably, coating composition as above and their any embodiment are substantially free of hydroxyl functional binder and hydroxyl-functional reactive diluent.More preferably, they are not containing hydroxyl functional binder and hydroxyl-functional reactive diluent.
Astoundingly, find that polyaspartate (A) and epoxy group(ing) and functionalized with alkoxysilane compound (C) can allow to reach wet fastness and adhering very big improvement containing the combination in the coating composition of polyisocyanates of the present invention, that is, the interlayer adhesion (such as after humidity/temperature strain and short period of time drying) between each layer is significantly improved; And after mixing polyisocyanate component (B) and component (A), the acceptable shelf life of at least one hour.Particularly can improve undercoat cohesive failure significantly.The outstanding alcohol resistance (such as ethanol, propyl carbinol, isopropylcarbinol and Virahol) that the coating obtained by described coating composition also has.
According in another embodiment, a kind of being used for carries out multi-layer coated method (1) to base material (especially vehicles body or vehicles body part), and described method (1) comprises the following steps:
1. at the layer applying primer coating compositions or primer surfacer coating composition alternatively on the base material of precoating;
2. on prime coat or primer surfacer layer, apply the layer of primary coating composition, described primary coating composition contains the pigment of color and/or special efficacy, and described primary coating composition is preferably water base primary coating composition;
2. on described undercoat, apply the Clear coating of Clearcoat coating composition; And
3. make described clearcoat layer cure, solidify together with described undercoat alternatively, at least one in wherein said primer coating compositions, described primer surfacer coating composition and described Clearcoat coating composition is according to coating composition mentioned above.
According to another embodiment, a kind of being used for carries out multi-layer coated method (2) to base material (especially vehicles body or vehicles body part), and described method (2) comprises the following steps:
1. at the layer applying primer coating compositions or primer surfacer coating composition alternatively on the base material of precoating;
2. on prime coat or primer surfacer layer, apply the layer of painted single-stage top coat layer; And
3. make described painted single-stage top coat layer solidification, solidify together with described prime coat or primer surfacer layer alternatively, wherein, at least one in described primer coating compositions, described primer surfacer coating composition and described painted single-stage top coat layer coating composition is coating composition mentioned above.
Each step of aforesaid method will be set forth in more detailed manner below.
Method (1): in step 1, primer coating compositions or primer surfacer coating composition are applied to alternatively on the base material of precoating.Suitable base material is metal and plastic basis material, particularly known in automobile industry base material, such as iron, zinc, aluminium, magnesium, stainless steel or their alloy, urethane, polycarbonate or polyolefine.Described base material can utilize such as electrodeposited primer to carry out precoating.Before applying primary coating composition, can be cured prime coat or primer surfacer layer or drying.But also can using wets touches the applying of wet technique.
In step 2, the undercoat of primary coating composition, preferably water base coating coating composition is applied on prime coat or primer surfacer layer.Primary coating composition is included in effect or pure color (solid colour) primary coating composition of conventional use in vehicles coating.
Primary coating composition can contain the conventional ingredient of pigmented basecoat coating composition, the pigment of such as color and/or special efficacy, filler, one or more tackiness agents, optionally linking agent, water and/or organic solvent and conventional paint additive.
The example of tackiness agent is conventional binder for film formation (film-forming binder), and when water base primary coating composition, the binder for film formation of water-dilutable be familiar with by those skilled in the art, the mishmash of the mishmash (hybrids) of such as vibrin, (methyl) acrylic copolymer resin or polyester/(methyl) acrylic copolymer and urethane resin or urethane/(methyl) acrylic copolymer.They can be reactive functional resin or non-functional resin.
Primary coating composition can through physical dryness or chemically crosslinked.Therefore, water base paint compositions can contain linking agent, such as, and polyisocyanate crosslinker.The selection of the linking agent used alternatively is depended on to the type of crosslinkable groups in tackiness agent, and known by those skilled in the art.
Preferably, water base primary coating composition comprises the urethane resin of water-dilutable, and alternatively with the resin of other water-dilutable, such as water-dilutable (methyl) acrylic copolymer combinationally uses, and uses with dispersant package.The example of the urethane resin of this water-dilutable is such as number-average molecular weight Mn is 500 grams/mol to 500000 grams/mol (preferably 1100 grams/mol to 300000 grams/mol, most preferably be 5000 grams/mol to 300000 grams/mol), acid number is the urethane resin of 10mg KOH/g to 100mg KOH/g (being preferably 20mg KOH/g to 80mg KOH/g).
Based on whole coating composition, described water base primary coating composition can be such as preferred to be less than 20wt%, particularly preferably contains conventional organic coating solvents with the ratio being less than 15wt%.
Upon application of described primary coating composition, particularly water base primary coating composition and carried out dry or solidification alternatively, then apply Clearcoat coating composition in the step 3 of method.Herein Clearcoat coating composition otherwise at undercoat under such as room temperature after dry or solidification, or after the of short duration flash distillation of undercoat, be applied to undercoat.
The coating of gained at room temperature can be solidified or at relatively high temperatures, such as at the most 80 DEG C, preferably to force to be cured at 40 DEG C to 60 DEG C.Such as, but the coating obtained also in higher temperature, can be cured at 80 DEG C to 160 DEG C.Solidification value depends primarily on used field and the type of linking agent.This coating composition, by ordinary method, preferably relies on spraying applying to apply.
Method (2): in step 1, as aforesaid method (1), primer coating compositions or primer surfacer coating composition are applied to alternatively on the base material of precoating.Carry out dry or solidification alternatively upon application of described primer coating compositions or primer surfacer coating composition, in the step 2 of method, apply painted single-stage top coat layer coating composition.
Can solidify as described in method (1) the coating that obtains.Described coating composition, by ordinary method, preferably relies on spraying applying to apply.
In this article, the coating composition considered and method can be used in automobile and industrial coating, but are particularly advantageous in vehicles washcoated.The solidification value used in vehicles washcoated is 20 DEG C to 80 DEG C, such as, and particularly 40 DEG C to 60 DEG C.Described coating composition also can be advantageously used in coating Large-sized Communication instrument and transport vehicle, as truck, motorbus and tramway, wherein, and the solidification value used at the most 80 DEG C or higher than 80 DEG C usually.In addition, except motor vehicle, this coating composition can be used for being coated with any industrial goods.
Based on the following example, the present invention will be set forth in further detail.Unless otherwise stated, all numbers and per-cent are all based on weight.
Embodiment
The preparation (not hydroxyl official energy tackiness agent) of Clearcoat coating composition
Utilize based on polyisocyanates
the activator of N3900 (asymmetrical HDI tripolymer, 100% solid substance, Bayer) activates based on aspartate
the Clearcoat coating composition of NH1420 (Bayer).Described activator through epoxy functional silane (purchased from figure new high-tech material advanced in years (Momentive Performance Materials)
a187) modification.Unmodified activator (not containing epoxy functional silane) is used to be used as comparative example.
Utilize the one-tenth shown in table 1 to assign to prepare clear coating composition (% by weight), and utilize the one-tenth shown in table 2 to assign to prepare activator (% by weight).
Table 1:
Table 2:
In each case, hand mix clear coating composition and activator is come with volume ratio 1:1.Gained coating composition have 61.5% solid content and actual VOC content lower than 3.5 lbs/gal (420 grams per liters) (comparative example: not containing the contrast activator of epoxy silane; Embodiment 1: use activator 1; Embodiment 2: use activator 2).
The galvanic deposit that utilizes sprayed to by activated clear coating composition on panel is coated with on commercially available pure red (azarin (Rouge vif)) single panel packing (1K) water base undercoat (the Elpo panel from ACT utilizing E-coat ED6100H to be coated with).Panel is coated with the two-pack primer surfacer be purchased, and before applying undercoat, toasts 30 minutes, and carry out sand milling at 60 DEG C.Before applying clear coating composition, at room temperature flash distillation undercoat 45 minutes.This undercoat is about 20 μm with build and is applied.This clear coating composition, under 20 DEG C/40%RH (relative humidity), utilizes
gTI ProLite spray gun (nozzle 1.3, gas cap TE20, gravity charging) applies with the coating of 2 intersections.50 μm are about to apply this Clear coating with build.At room temperature curing transparent coating one hour.
Before assessment adhesivity and high pressure cleaning, at room temperature make the panel of coating aging one week.
Table 3: dry adhesivity
| Comparative example | Embodiment 1 | Embodiment 2 | |
| X-grid (X-hatch) | 10 | 10 | 10 |
| #-grid (#-hatch) | 10 | 10 | 10 |
| Glossiness 20 ° | 87 | 87 | 87 |
| Obscure degree | 1 | 1 | 1 |
Table 4: be placed in the wet adhesion of humidity cabinet after 4 days
| comparative example | embodiment 1 | embodiment 2 | |
| x-grid | 10 | 10 | 10 |
| #-grid. | 0 (6) | 10 | 9 (6) |
| glossiness 20 ° | 85 | 85 | 85 |
Table 5: be placed in the wet adhesion of humidity cabinet after 10 days
| Comparative example | Embodiment 1 | Embodiment 2 | |
| X-grid | 5(6) | 10 | 10 |
| #-grid | 0(6) | 10 | 10 |
| Glossiness 20 ° | 84 | 84.5 | 86 |
| Obscure degree | 1.7 | 1.5 | 1.0 |
Based on wet adhesion after humidity cabinet, can find out, the laminated coating of the preparation that this result clearly illustrates that as contemplated herein has the adhesivity of improvement.Laminated coating prepared in accordance with the present invention does not demonstrate undercoat cohesive failure (cohesion failure).
In laminated coating as above, assess alcohol resistance, difference is to be applied to by clear coating composition on the water base undercoat of silver metal single component.
Table 6: alcohol resistance
| Comparative example | Embodiment 2 | |
| Ethanol | 1 | 9 |
| Propyl carbinol | 1 | 8 |
| Virahol | 8 | 10 |
Result clearly illustrates that, laminated coating prepared in accordance with the present invention has the alcohol resistance of improvement.
High pressure cleaning is assessed in laminated coating as above, wherein clear coating composition is applied on pure red (azarin (Rouge vif)) single packaging (IK) water base undercoat, on the water base undercoat of silver metal single component, and on single component red pearly-lustre water-base metal undercoat.
Table 7: high pressure cleaning
The performance of the high pressure resistant cleaning that the solidified coating display considered herein improves.
2. containing the preparation of the Clearcoat coating composition of extra hydroxyl functional binder
Based on 54.4%
n3900 (asymmetrical HDI tripolymer, 100% solid substance, Bayer) polyisocyanates and 45.6% n-butyl acetate, polyisocyanates activator is used to activate Clearcoat coating composition, described activator is not containing epoxy and silane-functional compound (=contrast activator), and use identical activator to activate Clearcoat coating composition, but extraly containing epoxy and silane-functional compound (=have purchased from figure new high-tech material advanced in years 1.66%
the activator 1 of A187).In each case, hand mix Clear coating formula and activator is come with volume ratio 1:1.Make NCO remain on 1.27 with the ratio of (NH+OH) always.
The one-tenth shown in table 8 is utilized to assign to prepare Clearcoat coating composition (CC1, CC2, comparative example (Comp.) CC2 and comparative example (CC3).
Table 8:
* as described belowly polyester is prepared:
According to US 6, the embodiment 8 of 277,497, prepares oligomer ester: 136 grams of MPE (monopentaerythritol) and 504 grams of methylhexahydrophthalic anhydrides are refluxed about one hour in 175 grams of BuAc (n-butyl acetate) as follows.Subsequently, add 480 grams of Racemic glycidol pivalates (glycidyl pivalate) and continue backflow gained mixture until acid number is lower than 1mg KOH/g.Add BuAc until reach theoretical solid content 75%.
* prepares acrylic copolymer as follows:
480 grams are loaded in the 4L tri-neck glass flask being equipped with agitator, contact thermometer, dropping funnel and condenser
100 (in aromatic hydrocarbon based mixtures, azeotropic point 164 DEG C, Exxon Corporation (Exxon)) and 309.6 grams of CARDURA's
(Hexion company (Hexion)), and heating with about 170 DEG C to 175 DEG C at backflow.Monomer/initiators mixtures be added to continuously in reaction content through 5 hours by dropping funnel, this monomer/initiators mixtures is by 708 grams of vinylbenzene, 708 grams of isobornyl methacrylates, 516 grams of 2-hydroxy methacrylate methacrylic esters, 158.4 grams of vinylformic acid, 60 grams of ditertiary butyl peroxides and 240 grams
composition.With 40 grams
100 rinse dropping funnel, and mixture is refluxed until obtain constant viscosity.Subsequently, with 780 grams of Methyl amyl ketone diluting reactor contents.Solid content is about 60%, and acid number is about 23mg KOH/g.
CC1: hydroxyl official can tackiness agent
CC2: hydroxyl functional polyester, aspartate: the ratio of polyester is 75:25 (solid substance is than solid substance)
Comparative example CC2: hydroxyl functional polyester, aspartate: the ratio of polyester is 50:50 (solid substance is than solid substance)
Comparative example CC3: hydroxyl functional acrylic analog copolymer, aspartate: the ratio of acrylic copolymer is 50:50 (solid substance is than solid substance)
Table 9:
| CC1 | CC2 | Comparative example CC2 | Comparative example CC3 | |
| Activator 1 | Activator 1 | Activator 1 | Activator 1 | |
| Initial spray viscosity | 13” | 13.4” | 14.4” | 18” |
| Viscosity after 15 minutes | 14” | 20” | 20” | 60” |
| Viscosity after 20 minutes | 16” | 23” | 23” | - |
| Shelf life | 50min. | 15-20min. | <15min. | <<15min. |
At 20 DEG C, in DIN4 cup, measure spray viscosity.
Result in table 9 shows, when comparative example CC2 and comparative example CC3, initial spray viscosity increases, and significantly reduces shelf life.
In addition, blended (comparative example CC2 and the comparative example CC3) of aspartate and hydroxyl-functional polyester or acrylic copolymer remarkable yellow (table 10) of causing Clear coating to be filled a prescription.On BYK (Bi Ke chemistry) LCSIII device, in Hazen (black once colourity) yardstick (based on ASTM D1209), measure the color (table 10) of Clear coating formula.
Table 10:
| CC1 | CC2 | Comparative example CC2 | Comparative example CC3 | |
| Initially | 76 | 73 | 70 | 98 |
| 2 weeks are stored at 49 DEG C | 106 | 132 | 121 | 604 |
| 4 weeks are stored at 49 DEG C | 146 | 177 | 223 | >1000 |
The at room temperature aging adhesivity (dry adhesivity and wet adhesion) evaluating coating for a week afterwards.As described in Example 1, the single component utilizing pure red (azarin (Rouge vif)) to be purchased water base base paint coating panel.
Table 12: dry adhesivity
| CC1 | CC2 | CC1 | CC2 | |
| Contrast activator | Contrast activator | Activator 1 | Activator 2 | |
| X-grid | 10 | 10 | 10 | 10 |
| #-grid | 10 | 10 | 10 | 10 |
Table 13: be placed in the wet adhesion of humidity cabinet after 10 days
| CC1 | CC2 | CC1 | CC2 | |
| Contrast activator | Contrast activator | Activator | Activator 1 | |
| X-grid | 5(6) | 10 | 10 | 10 |
| #-grid | 0(6) | 9(6) | 10 | 10 |
| DOI | 94 | 84 | 91 | 80 |
| Obscure degree | 1.4 | 8.1 | 3.7 | 11.4 |
Result shows, after being placed in humidity cabinet, can find out based on wet adhesion, and the laminated coating utilizing the activator of epoxy silane modification (activator 1) to prepare according to the present invention has the adhesivity of improvement.The clear coating composition of comparative example demonstrates due to undercoat cohesive failure can not received adhesivity.
Testing method:
Shelf life (Pot life): by measuring the increase as the viscosity of the function of time, measure the shelf life of composition.Be defined as initial viscosity shelf life and increase time needed for 1.5 times.Define the time period that clear coating composition is still easy to spray shelf life.
Adhesivity: this method of testing is based on ASTM D2247-92 and ASTM D3359-92A.
Cross-hatching adhesive tape test (cross-cut tape test) (X-grid) is utilized to assess dry adhesivity and wet adhesion.Carry out manufacture grid with manual cross cut test device, its center line is separated by 1mm (#-grid).Brush this panel gently to remove any disengaging fragment in coating.In order to ensure the good contact with film, be placed on by scotch tape on grid, blend rubber is wiped and is carried out swiping to guarantee good contact.After applying adhesive tape 60 seconds in 120 seconds, catch the free end of adhesive tape only so that this adhesive tape may be retracted rapidly with the angle close to 180 degree, thus remove this adhesive tape.
According to damage intensity (being represented by the performance of shooting), dry adhesivity is rated the rank of 0 (damaging completely) to 10 (without damaging).
For the evaluation of wet adhesion, use identical method, but in the method, panel to be placed in humidity cabinet (100% relative humidity (RH) and 40 DEG C) 4 days and 10 days.
Also have evaluated with the destruction of Types Below (shown between slash):
1: base material/coating destroys
2: priming paint/top coat layer destroys
3: basecoat/clearcoat layers is destroyed
4: priming paint/Primer failure
5: priming paint cohesive failure
6: undercoat cohesive failure
High pressure resistant clean (HPC, High pressure cleaning) property: carry out this test according to the testing method based on Volvo specification (STD 423-0015).
Before the adhering high pressure resistant cleaning of test reflection, the line utilizing the marking tool with flat tooth steel to mark two 0.5 millimeter on test panel damages to make initial point.The line marked is drawn downwards to base material in the mode at right angle each other to form right-angled intersection.
At the temperature of 50 DEG C and under the pressure of 150 bar, during 20 seconds, water is sprayed on the panel (d=4cm) of damage.Distance between rifle and panel reaches 15cm.
After test completes, dry panel and the degree of paint damage is graded.Represent with the % of the coating removed from panel, wherein 0% is best.The type (identical with adhering explanation) of destruction is referred in bracket.
Alcohol resistance: this testing method is based on ISO2812-4.The object of this testing method is the alcohol resistance of characterizing coating.Before test, test panel is limited to lower 16 hours of standard conditions (23 ± 2 DEG C and 50 ± 5% relative humidity).Several alcohols are placed on described panel, and cover with a small pieces filter paper and watch glass (watch glass).All panels with spot (spot) to be spent the night stop.Wash this panel with water, wipe water subsequently.Spot in inspection panel, and compare with non-exposed region:
A. swelling; B. little loss of gloss; C. color change; D. deliquescing; E. other deviation.
Any change in the character of film is all unacceptable.
Use following graded scale:
The sign of 10=immaculate or distortion
9=almost can't detect spot or distortion
The annular (slight ring) that 8=is slight
The variable color that 7=is very slight or slight distortion
The glossiness forfeiture that 6=is slight or slight variable color
5=glossiness is obviously lost or variable color
4=slight erosion or be obviously out of shape
3=slightly heaves, obviously corrosion or variable color
2=obviously heaves
1=film dissolves
Glossiness: utilize micro-TRI glossiness device of Bi Ke Gartner company (Byk Gardner) (Germany) to measure.Reflected light is measured with the angle of 20 °.
Obscure degree: utilize the WaveScan-DOI device of Bi Ke Gartner company (Byk Gardner) (Germany) to measure.Be less than the structure influence visually-perceptible of 0.1mm, and therefore, WaveScan-DOI utilizes CCD camera to measure the scattered light caused by these microtextures.The parameter measured by this way is called as " obscure degree (dullness) " of coating.The obscure degree (with 1 for minimum value) of lower value is preferred.
Although illustrated at least one illustrative embodiments in detailed description above, should be understood that also there is multiple modification.It is to be further understood that illustrative embodiments or multiple exemplary embodiment are only example, and be not meant to limit the scope of the invention by any way, practicality or structure.On the contrary, above be specifically described as the convenient road map figure that those skilled in the art provide exemplifying embodiment embodiment, should be understood that, do not depart from the present invention as claim require or its legal equivalents scope under, various change can be carried out to the function of key element described in illustrative embodiments and layout.
Claims (16)
1. a coating composition, described composition comprises:
A) at least one polyaspartate;
B) at least one has the polyisocyanate crosslinker of free isocyanate groups; And
C) at least one has the compound of at least one epoxy group(ing) and at least one alkoxysilane group.
2. coating composition according to claim 1, wherein, described at least one polyaspartate A) be the compound of formula (I)
Wherein, X represents the n-valency organic group that the amino by removing on uncle's polyamines or polyetheramine obtains; R1 and R2 is the identical or different organic group to isocyanate group inertia; R3, R4 and R5 are identical or different, and represent hydrogen or the organic group to isocyanate group inertia; And n represents that at least value is the integer of 2.
3. coating composition according to claim 2, wherein, n is 2 or 3.
4. coating composition according to any one of claim 1 to 3, wherein, described at least one has the Compound C of at least one epoxy group(ing) and at least one alkoxysilane group) be the compound of formula (III):
Wherein, Z represents that m is the residue of 1 to 4
or represent 3,4-epoxycyclohexyl; R6, R7, R8 are the identical or different organic residue with 1 to 30 carbon atom, and prerequisite is at least one in residue R6, R7 and R8 is the alkoxyl group with 1 to 4 carbon atom; And n is 2,3 or 4.
5. coating composition according to claim 4, wherein, R6, R7 and R8 represent the identical or different alkoxyl group with 1 to 4 carbon atom independently of each other.
6. coating composition according to any one of claim 1 to 5, wherein, relative to component A) and B component) the summation of solid content, with solid substance weighing scale, described coating composition comprises the component C of 0.25wt% to 5.0wt%).
7. coating composition according to any one of claim 1 to 6, wherein, described coating composition is not containing hydroxyl functional binder.
8. coating composition according to any one of claim 1 to 7, wherein, described coating composition is containing closing amine.
9., for carrying out a multi-layer coated method to base material, said method comprising the steps of:
1) at the layer applying primer coating compositions or primer surfacer coating composition alternatively on the base material of precoating;
2) on prime coat or primer surfacer layer, apply the layer of primary coating composition, described primary coating composition contains the pigment of color and/or special efficacy;
3) on described undercoat, apply the Clear coating of Clearcoat coating composition; And
4) described clearcoat layer cure is made, solidify together with described undercoat alternatively, wherein, at least one in described primer coating compositions, described primer surfacer coating composition and described Clearcoat coating composition is coating composition according to any one of claim 1 to 8.
10., for carrying out a multi-layer coated method to base material, said method comprising the steps of:
1) at the layer applying primer coating compositions or primer surfacer coating composition alternatively on the base material of precoating;
2) on prime coat or primer surfacer layer, apply the layer of painted single-stage top coat layer; And
3) make described painted single-stage top coat layer solidification, solidify together with described prime coat or primer surfacer layer alternatively,
Wherein, at least one in described primer coating compositions, described primer surfacer coating composition and described painted single-stage top coat layer coating composition is coating composition according to any one of claim 1 to 8.
11. methods according to claim 9, wherein, described primary coating composition is water base primary coating composition.
12. methods according to any one of claim 9 to 11, wherein, described base material is vehicles body or vehicles body part.
Coating composition according to any one of 13. claims 1 to 8 is as the application of primer coating compositions, primer surfacer coating composition, painted single-stage top coat layer coating composition or Clearcoat coating composition.
The application of coating composition according to any one of 14. claims 1 to 8 in vehicles washcoated.
The application be applied in vehicles washcoated of 15. claims 13.
The application of method according to any one of 16. claims 9 to 12 in vehicles washcoated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361773373P | 2013-03-06 | 2013-03-06 | |
| US61/773,373 | 2013-03-06 | ||
| PCT/US2014/020283 WO2014138052A1 (en) | 2013-03-06 | 2014-03-04 | Two-component coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105008424A true CN105008424A (en) | 2015-10-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480012501.XA Pending CN105008424A (en) | 2013-03-06 | 2014-03-04 | Two-component coating composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20160032142A1 (en) |
| CN (1) | CN105008424A (en) |
| DE (1) | DE112014001170T5 (en) |
| WO (1) | WO2014138052A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382644A (en) * | 2017-03-07 | 2019-10-25 | 旭化成株式会社 | Poly-aspartate coating composition, film and coated article |
| CN111848950A (en) * | 2020-07-06 | 2020-10-30 | 深圳飞扬兴业科技有限公司 | Silicon-modified aspartate polyurea and preparation method and application thereof |
| CN114539878A (en) * | 2022-03-03 | 2022-05-27 | 湖北三棵树新材料科技有限公司 | Special water-based epoxy paint for wet-on-wet and preparation method thereof |
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| CN104312398B (en) * | 2014-10-22 | 2016-08-17 | 武汉长江科创科技发展有限公司 | Polyureas-polysiloxanes organic inorganic hybridization concrete biological pollution protective material and preparation method thereof |
| WO2016064481A1 (en) * | 2014-10-22 | 2016-04-28 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Two-component siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes |
| MX2020001582A (en) * | 2017-08-09 | 2020-07-13 | Basf Coatings Gmbh | Two-component (2k) clearcoat and method to coat a substrate with the two -component (2k) clearcoat having enhanced visual appearance. |
| EP3489316A1 (en) * | 2017-11-22 | 2019-05-29 | Covestro Deutschland AG | New systems for priming and bonding of flooring materials |
| DE102020005446A1 (en) * | 2020-09-07 | 2022-03-10 | Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) | Improved Fillers and Methods for Coating Large Structural Components |
| WO2023117034A1 (en) | 2020-12-17 | 2023-06-29 | Akzo Nobel Coatings International B.V. | Multi-layer coating system for polycarbonate substrates |
| EP4198094A1 (en) | 2021-12-20 | 2023-06-21 | Covestro Deutschland AG | Multilayer structure on metal substrates based on polyaspartate coatings |
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- 2014-03-04 WO PCT/US2014/020283 patent/WO2014138052A1/en active Application Filing
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| CN114539878A (en) * | 2022-03-03 | 2022-05-27 | 湖北三棵树新材料科技有限公司 | Special water-based epoxy paint for wet-on-wet and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112014001170T5 (en) | 2015-11-19 |
| US20160032142A1 (en) | 2016-02-04 |
| WO2014138052A1 (en) | 2014-09-12 |
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Application publication date: 20151028 |